EP2672817B1 - Formulations insecticides améliorées - Google Patents

Formulations insecticides améliorées Download PDF

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Publication number
EP2672817B1
EP2672817B1 EP12744477.6A EP12744477A EP2672817B1 EP 2672817 B1 EP2672817 B1 EP 2672817B1 EP 12744477 A EP12744477 A EP 12744477A EP 2672817 B1 EP2672817 B1 EP 2672817B1
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Prior art keywords
insecticide
amine
oil phase
aqueous phase
formulation
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EP12744477.6A
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German (de)
English (en)
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EP2672817B2 (fr
EP2672817A4 (fr
EP2672817A2 (fr
Inventor
Dennis G. Wujek
Raymond E. Boucher
Martin C. Logan
Stephen L. Wilson
Mei Li
Lorenzo AULISA
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Corteva Agriscience LLC
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Dow AgroSciences LLC
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Application filed by Dow AgroSciences LLC filed Critical Dow AgroSciences LLC
Priority to PL12744477T priority Critical patent/PL2672817T5/pl
Priority to DK17179584.2T priority patent/DK3251507T3/da
Priority to PL17179584T priority patent/PL3251507T3/pl
Priority to EP17179584.2A priority patent/EP3251507B1/fr
Publication of EP2672817A2 publication Critical patent/EP2672817A2/fr
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/26—Phosphorus; Compounds thereof

Definitions

  • Various aspects and embodiments relate generally to formulations of insecticide formulations that exhibit advantageous biological, commercial and/or environmental properties.
  • Controlling insect population is essential to modem agriculture, food storage, and hygiene.
  • safe and effective encapsulated insecticidal formulations play a significant role in controlling insect populations.
  • Properties of useful encapsulated insecticidal formulations include good efficacy against targeted pests, including good initial toxicity against targeted insects, ease of handling, stability, advantageous residence times in the environment and, in some instances, a long effective period of insecticidal activity after its application to an area adjacent to a population of insects.
  • Formulations comprising microencapsulated chlorpyrifos have been described in WO 2010/101821 A1 and by L. Zhu et al. in J. Pestic. Sci. 2010, 35(3), 339-343 .
  • Embodiments of the present disclosure include insecticide formulations.
  • Such insecticide formulations include a polymer shell formed from a mixture comprising a cross-linking amine selected from the group consisting of ethylenediamine (EDA), tetramethylenediamine and 1,2-cyclohexyldiamine, and a hydrophobic isocyanate monomer, where the molar ratio of amine to isocyanate groups in the mixture is between 0.3 to 1 and 0.8 to 1, and an insecticide at least partially encapsulated by the polymer shell.
  • EDA ethylenediamine
  • tetramethylenediamine 1,2-cyclohexyldiamine
  • hydrophobic isocyanate monomer where the molar ratio of amine to isocyanate groups in the mixture is between 0.3 to 1 and 0.8 to 1, and an insecticide at least partially encapsulated by the polymer shell.
  • Embodiments of the present disclosure also include insecticide formulations formed by a process that includes forming an organic (i.e., oil) phase consisting of a hydrophobic monomer, at least one insecticide composition, a solvent, and a preservative, combining the organic phase with an aqueous phase to form a dual-phase mixture and combining at least one of the above cross-linking amines with the mixture to form the insecticide capsule formulation.
  • an organic (i.e., oil) phase consisting of a hydrophobic monomer, at least one insecticide composition, a solvent, and a preservative, combining the organic phase with an aqueous phase to form a dual-phase mixture and combining at least one of the above cross-linking amines with the mixture to form the insecticide capsule formulation.
  • Embodiments of the present disclosure further include methods of forming insecticide formulations.
  • the methods may include forming an organic phase consisting of a hydrophobic monomer, at least one insecticide composition, a solvent, and a preservative, combining the organic phase with an aqueous phase to form a mixture and combining at least one of the above cross-linking amines with the mixture to form the insecticide capsule formulation.
  • Embodiments of the present disclosure further include methods of extending the effective field life of an insecticide.
  • Such methods may include combining the insecticide, a cross-linking amine as defined above, and at least one isocyanate monomer, the cross-linking amine and the at least one isocyanate monomer are present in concentrations such that the molar ratio of the cross-linking amine to isocyanate groups contained in the mixture is between 0.3:1 and 0.8:1, and forming a polymer shell that at least partially encapsulates a portion of the insecticide.
  • Embodiments of the present disclosure further include a stable aqueous insecticide formulation that includes a) a microcapsule, having a water insoluble polyurea shell wall prepared by an interfacial polycondensation reaction between a water soluble cross-linking amine as defined above and an oil soluble isocyanate monomer in which (i) the molar ratio of amine to isocyanate groups is between 0.3 to 1 and 0.8 to 1, (ii) the polyurea shell has a thickness of greater than 2 nanometers (nm) and less than 50 nm, (iii) the average particle size is from 1 micrometer ( ⁇ m) to 30 ⁇ m, and (iv) containing an inner liquid core comprised of an insecticide at least partially encapsulated by the polymer shell; and b) a continuous aqueous phase.
  • a stable aqueous insecticide formulation that includes a) a microcapsule, having a water insoluble polyurea shell wall prepared by an interfacial polyconden
  • FIG. 1 is a bar graph showing degradation of chlorpyrifos-methyl in insecticide formulations formed according to embodiments of the methods of the present disclosure.
  • encapsulate means and include to surround, encase, or protect in a capsule.
  • microcapsule means and includes a particle(s) of the insecticide encapsulated within a polymeric material, such as polyurea.
  • shell and wall mean and include an assembly of a polymeric material, such as polyurea, disposed on or encapsulating a surface of a core including an insecticide. Such terms do not necessarily imply that a given shell or wall is completely uniform or that it completely encompasses whichever materials or components that are localized within the corresponding microcapsule.
  • chlorpyrifos-methyl refers to O,O-dimethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate.
  • Embodiments of insecticidal formulations include an insecticide at least partially encapsulated within a polyurea shell (i.e., a microcapsule).
  • the insecticide within the shell may be present as a stable aqueous capsule suspension of an organophosphate insecticide (e.g., chlorpyrifos-methyl).
  • the insecticidal formulations provide effective pest control with improved chemical and physical stability.
  • the insecticidal formulations may effectively kill or repel insects for at least 14 days after their application.
  • Such improved stability may be obtained by using a cross-linking amine and an isocyanate monomer to form the microcapsule polyurea shell where the molar ratio of amine:isocyanate groups is between 0.3:1 and 0.8:1.
  • Methods of forming the insecticidal formulations and methods of controlling (e.g., repelling, inhibiting or killing) pests using the insecticidal formulations are also disclosed.
  • the insecticide may include at least one organophosphate insecticide, such as, acephate, azinphos-methyl, chlorfenvinphos, chlorethoxyfos, chlorpyrifos, diazinon, dimethoate, disulfoton, ethoprophos, fenitrothion, fenthion, fenamiphos, fosthiazate, malathion, methamidophos, methidathion, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phorate, phosmet, profenofos, and/or trichlorfon.
  • the ingredient having the insecticidal activity may be chlorpyrifos-methyl.
  • Chlorpyrifos-methyl which is the common name for O,O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate, is a well-known insecticide that has been show to be effective against a broad spectrum of pests.
  • Chlorpyrifos-methyl is a crystalline organophosphate insecticide that acts as an acetylcholinesterase inhibitor, killing insects by interfering with the function of the nervous system.
  • insecticide compositions including chlorpyrifos-methyl are marketed by Dow AgroSciences LLC (Indianapolis, IN) under the trade name RELDAN®.
  • the shell that at least partially encases the insecticide may be formed by a reaction (e.g., an interfacial polycondensation reaction) between at least one monomer that is essentially insoluble in water (i.e., a hydrophobic monomer) and at least one monomer that is soluble in water (i.e., a hydrophilic monomer).
  • a reaction e.g., an interfacial polycondensation reaction
  • hydrophobic monomers that may be used to form the shell of the microcapsule include isocyanates, diisocyanates, polyisocyanates, diacid chlorides, poly acid chlorides, sulfonyl chlorides and chloroformates.
  • the term isocyanate as used herein may include isocyanates, diisocyanates, polyisocyanates and mixtures thereof.
  • the hydrophobic monomer may be an isocyanate such as PAPI® 27 polymethylene polyphenylisocyanate, which is marketed by Dow Chemical
  • hydrophilic monomers examples include cross-linking amines such as diamines and polyamines.
  • the capsule forming reaction is carried out in the presence of a cross-linking amine selected from the group consisting of ethylenediamine (EDA), tetramethylenediamine and 1,2-cyclohexyldiamine.
  • a polyurea shell may be formed by reacting a hydrophobic isocyanate monomer and the cross-linking amine.
  • the cross-linking amines used to form the shell of the microcapsule are selected from the group consisting of ethylenediamine (EDA), and 1,2-cyclohexyldiamine.
  • the cross-linking amine may hasten shell formation. While not wishing to be bound by any particular theory, it is believed that the cross-linking amine may also degrade the organophosphate insecticide during the shell forming reaction.
  • the molar ratio of amine:isocyanate groups in the mixture used to prepare the insecticide formulation is between 0.3:1 and 0.8:1.
  • the molar ratio of amine:isocyanate groups in the mixture used to prepare the insecticide formulation may be 0.7:1.
  • the insecticide formulations may be prepared, for example, using an emulsion polymerization process that includes combining an aqueous phase that includes the hydrophilic monomer (e.g., the cross-linking amine) into an organic phase that includes the hydrophobic monomer (e.g., the isocyanate) and the insecticide.
  • the hydrophobic monomer and the hydrophilic monomer are reacted to form a polymeric shell around a core of the insecticide dispersed within a liquid.
  • the insecticide formulations may be prepared by a batch process, an in-line or continuous process or a combination of the two. Such processes may be designed, optimized to the desired output parameters and operated by one of ordinary skill in the art.
  • the aqueous phase may be prepared by dissolving one or more additives, which may be included in the aqueous phase of the insecticide formulations.
  • additives may include one or more surfactants and preservatives.
  • An example of a suitable surfactant includes polyvinyl alcohol (PVA), such as GOHSENOLTM GL03 polyvinyl alcohol, which is commercially available from Nippon Synthetic Chemical Industry Co. (Osaka, Japan).
  • An example of a suitable preservative includes PROXEL® GXL preservative (Arch UK Biocides Limited, England).
  • GOHSENOLTM GL03 polyvinyl alcohol and PROXEL® GXL preservative may optionally be added to the aqueous phase.
  • the organic or oil phase may be formed by combining PAPI® 27 polymethylene polyphenylisocyanate with a solution of the chlorpyrifos-methyl in a solvent.
  • the solvent may be a hydrocarbon fluid, such as SOLVESSO® 150 ND, which is a mixture of aromatic hydrocarbons with a distillation temperature range of between about 185°C and about 207°C that is commercially available from Exxon Mobile Chemical Company (Houston, TX).
  • the solution of the chlorpyrifos-methyl in the solvent may be formed to include 50 wt% of the chlorpyrifos-methyl in the SOLVESSO® 150 ND.
  • a commercially available composition of chlorpyrifos-methyl may also be used in the organic phase.
  • Such compositions, such as RELDAN® insecticide, which is marketed by Dow AgroSciences LLC may include between 10 wt% and 30 wt% of the chlorpyrifos-methyl.
  • the organic phase may also include a preservative, such as 1-nonanal.
  • a preservative such as 1-nonanal.
  • the ingredients of the organic phase may be mixed until a substantially homogenous suspension is obtained.
  • the aqueous phase and the organic phase may be combined to form a mixture that includes two immiscible phases (i.e., a dual-phase mixture).
  • the dual-phase mixture may be subjected to a conventional high shear emulsification process to disperse the oil phase into the aqueous phase.
  • a desired particle size i.e., the volume mean diameter of the particles
  • the particle size may be controlled by adjusting at least one of a length of time or a speed at which the mixture is subjected to emulsification.
  • the particle size may be between 1 micron ( ⁇ m) and 30 ⁇ m and, more particularly, between 1 ⁇ m and 10 ⁇ m.
  • the cross-linking amine such as the EDA
  • the cross-linking amine may then be added to the emulsion and may react with isocyanate groups of the hydrophobic monomer, such as the PAPI® 27 polymethylene polyphenylisocyanate, at an interface between the oil phase particles and the aqueous phase to form the microcapsule polyurea shell.
  • the molar ratio of amine to isocyanate groups in the mixture may be between 0.3:1 and 0.8:1 and, more particularly, between 0.5:1 and 0.7:1.
  • the mixture maybe maintained at a temperature of between 20°C and 60°C and, more particularly, between 20°C and 30 °C.
  • the resulting insecticidal capsule formulation is a microcapsule suspension that includes the oil phase liquid particles at least partially encapsulated by the shell and suspended in the aqueous phase.
  • the oil phase particles may be referred to herein as the "core" of the microcapsules.
  • the shell of the microcapsules may comprise a polyurea. By adjusting the length of time during which the mixture is subjected to emulsification and/or a speed of mixing, a thickness of the polyurea shell may be varied. Similarly, the amounts of isocyanate, cross-linking amines, and other ingredients may be adjusted to form capsules with varying sizes and shell thicknesses.
  • the processing method used to prepare the insecticide formulations may be a combination of a batch process and a continuous, in-line emulsification process.
  • the organic and aqueous phases may be prepared as described herein and may then be individually metered into an inline rotor/stator homogenizer, or similar device, at an aqueous to oil volume ratio of 0.75 to 1.10.
  • the size of the emulsion oil droplet formed may be controlled by the feed rates into the homogenizer and the rotational speed of the homogenizer.
  • the particle size may be between 1 ⁇ m and 30 ⁇ m and, more particularly, between 1 ⁇ m and 10 ⁇ m.
  • the cross-linking amine solution may then be added in-line to the out-flow of the emulsion from the homogenizer using another metering system to add the second component for the polyurea shell formation.
  • the resulting stream may then be collected into a finishing vessel where any finishing agents, as described herein, may be added to complete the formulation.
  • the PAPI 27 isocyanate may alternatively be added as a separate stream to the homogenizer by adding another metering system.
  • the processing described herein may be designed, optimized and operated by one of ordinary skill in the art.
  • m C m O -m OSM
  • m S m O +( f WSM / OSM )) m OSM - m C
  • f WSM / OSM m WSM / M OSM (a ratio of hydrophilic monomer to hydrophobic monomer)
  • m O is a total mass of the oil components (e.g., the chlorpyrifos-methyl, the solvent and the hydrophobic monomer)
  • m OSM is the mass of the hydrophobic monomer
  • m WSM is the mass of the hydrophilic monomer
  • the insecticidal formulations may be formed such that the shell of each microcapsule has an average thickness of between 2 nanometers (nm) to 50 nm and, more particularly, between 2 nm to 20 nm.
  • an average thickness of the shells may be 10 nm.
  • finishing agents may be added to the insecticidal capsule formulation.
  • Such finishing agents include, for example, one or more surfactants, thickeners, preservatives, antifoaming agents and buffers.
  • suitable surfactants include a graft copolymer of alkylphenolethoxylate and polyalkyleneglycoletheracryl, such as that commercially available from Croda Chemicals Ltd. (England) under the trade name ATLOXTM 4913 polymeric surfactant, GEROPON® sodium dioctyl sulfosuccinate (SDS), which is commercially available from Rhodia Novecare (Canbury, NJ) and GOHSENOLTM GL03 polyvinyl alcohol.
  • Suitable thickeners include xanthan gum (e.g., KELZAN® ASX xanthan gum, which may be obtained commercially from CP Kelco U.S., Inc., Atlanta, GA), a microcrystalline cellulose gel, such as AVICEL® CL 611, which is commercially available from FMC Corporation (Philadelphia, PA) and silicates (e.g., VEEGUM® magnesium aluminum silicate, which may be obtained commercially from R.T. Vanderbilt Company, Inc., Norwalk, CT).
  • xanthan gum e.g., KELZAN® ASX xanthan gum, which may be obtained commercially from CP Kelco U.S., Inc., Atlanta, GA
  • AVICEL® CL 611 which is commercially available from FMC Corporation (Philadelphia, PA)
  • silicates e.g., VEEGUM® magnesium aluminum silicate, which may be obtained commercially from R.T. Vanderbilt Company, Inc., Norwalk, CT
  • GOHSENOLTM GL03 polyvinyl alcohol, VEEGUM® magnesium aluminum silicate, KELZAN® ASX xanthan gum, and PROXEL® GXL preservative may optionally be added to the aqueous phase after formation of the insecticidal capsule suspension.
  • suitable antifoaming agents includes silicone-based anti-foaming agents.
  • Such a silicon-based antifoaming agent is available from Harcros Chemicals, Inc. (Kansas City, KS) under the trade name Antifoam 100 IND.
  • the buffer may include, for example, an aqueous solution of a weak acid and its conjugate base or a weak base and its conjugate acid.
  • the buffer solution may be formulated to maintain a desired pH of the insecticide formulation.
  • the aqueous insecticidal capsule formulations may be optionally diluted in a carrier such as water and applied directly to, or to a surface adjacent to, a population of insects.
  • the insecticidal formulations may be as effective against pests as the non-encapsulated formulations, but in comparison, may exhibit significantly reduced toxicity to mammals, less environmental impact, and enhanced stability. Furthermore, the insecticidal formulations may maintain their insecticidal properties for a substantially increased time period in comparison to non-encapsulated formulations, especially liquid based formulations.
  • formulations of insecticides such as chlorpyrifos-methyl
  • an inert liquid such as a hydrocarbon fluid and 1-nonanal.
  • Various insecticidal formulations were prepared with different amounts of EDA in a continuous or in-line process as described herein.
  • Example Insecticidal Capsule Formulations Formulation 1 2 8 11 Chlorpyrifos-methyl 19.4 19.4 19.4 19.4 SOLVESSO® 150 ND hydrocarbon fluid 19.0 19.0 19.0 1-nonanal 0.38 0.38 0.38 0.38 0.38 PAPI® 27 polymethylene polyphenylisocyanate 0.6231 0.6231 0.6231 0.6231 Ethylenediamine (EDA) 0.1604 0.1395 0.1256 0.0977 GOHSENOLTM GL03 polyvinyl alcohol 1.9886 1.9886 1.9886 1.9886 1.9886 GEROPON® SDS 0.2448 0.2448 0.2448 0.2448 AVICEL® CL 611 stabilizer 0.11 0.11 0.11 0.11 KELZAN® ASX xanthan gum 0.02 0.02 0.02 0.02 PROXEL® GXL preservative 0.05 0.05 0.05 0.05 0.05 Antifoam 100 IND 0.0756 0.0756 0.0756 0.0756 Deionized (DI) water 34.7 34.7
  • the aqueous phase was prepared by stirring together materials to make a 6.0 wt% polyvinyl alcohol solution (GOHSENOL® GL03), containing 0.15 wt% Proxel GXL with water as the balance ingredient.
  • the organic or oil phase was prepared by stirring together 49.2% chlorpyrifos-methyl, 1.0% 1-nonanal, 48.2% Solvesso 150 and 1.6% PAPI 27.
  • the cross-linking amine phase was prepared by dissolving EDA to make 2.0 wt% solution in water.
  • the Kelzan gel phase contained 1.5 wt% Kelzan ASX, 0.1 wt% Proxel GXL and 98.4% water and was prepared using the recommended manufacturer's guideline for high shear dispersion.
  • the Avicel gel phase contained 5.0 wt% Avicel C-611, 0.1 wt% Proxel GXL and 94.9 wt% water dispersed together using high speed dispersion equipment.
  • the buffer solution was prepared by mixing 50 mL of 0.1M potassium dihydrogen phosphate (KH 2 PO 4 ) and 29.1 mL or 0.1M sodium hydroxide (NaOH) and bringing the solution to a final 100 mL volume with deionized water.
  • the in-line encapsulation system consisted of 3 metering pumps. Each pump was calibrated to deliver a fixed rate of material: 41.5 gram per minute (gpm) oil phase, 35.0 gpm aqueous phase and 2.9 gpm of the amine solution.
  • the oil phase and aqueous phase pumps were combined at the inlet to an IKA DK-25 rotor/stator homogenizer which created the emulsion.
  • the DK-25 had adjustable speed and a tachometer to permit fine particle size control. Typically, the DK-25 was operated at about 18,000 RPM.
  • the EDA solution was metered into the liquid stream at the discharge of the homogenizer and passed through a 5 element static mixer and collected in a vessel.
  • the rate of flow of the EDA solution was varied as needed to provide the desired ratio for each formulation.
  • the formulation was finished by stirring for at least 30 minutes, then adding in the GEROPON® SDS, the Antifoam 100 IND, the Kelzan and Avicel gel phases, the optional buffer solution, if used, and finally water as needed.
  • a final brief homogenization was performed to incorporate the finishing agents into the capsule suspension.
  • the molar ratios of amine:isocyanate groups in the emulsions containing EDA and polyisocyanate PAPI® 27 used to prepare comparative formulations 1, 2 and 8 and formulation 11 according to the invention are respectively 1.15:1, 1.0:1, 0.9:1 and 0.7:1.
  • compositions formed from the ingredients listed in Table 1 were determined over time.
  • the properties evaluated were pH, particle size, viscosity and syneresis. Such properties were determined immediately after formation ("Initial”).
  • Samples of each of the comparative formulations 1, 2 and 8 and formulation 11 according to the invention were stored at 54°C, 40°C, freezing temperature (FT, about 0°C) and room temperature (RT, about 25°C).
  • the properties of the samples stored at 54°C, 40°C, FT and RT were determined after 2 weeks and the properties of the samples stored at 40°C and RT were determined after 4 weeks.
  • Tables 1 through 5 provide data showing a comparison of each of the properties of comparative formulations 1, 2 and 8 and formulation 11 according to the invention observed after storing each of the formulations as described.
  • the pH of the samples of comparative formulations 1, 2 and 8 and formulation 11 according to the invention stored at different temperatures for time periods of 2 weeks and 4 weeks were determined using conventional methods.
  • a comparison of the pH of comparative formulations 1, 2 and 8 and formulation 11 according to the invention of the initial formulations and the samples stored at different temperatures for time periods of 2 weeks and 4 weeks are shown in Table 2.
  • Table 2 the change in pH in each comparative formulations 1, 2 and 8 and formulation 11 according to the invention was substantially consistent in the samples stored under substantially the same conditions.
  • the molar ratio of amine:isocyanate groups used to prepare each of comparative formulations 1, 2 and 8 and formulation 11 according to the invention did not appear to greatly impact the pH level in the formulations as the differences were generally within a range of about 1 pH unit.
  • Table 2 Determination of pH of Insecticidal Capsule Formulations Formulation Time Temperature 1 2 8 11 Initial RT 7.3 7.1 6.7 6.1 2 weeks 54°C 4.2 3.9 4.1 4.2 2 weeks 40°C 6.4 6.2 6.0 5.6 2 weeks FT 7.0 6.8 6.5 5.9 2 weeks RT 7.1 7.0 6.6 6.1 4 weeks 40°C 5.6 5.5 5.4 5.2 4 weeks RT 7.0 6.8 6.5 5.9
  • Particle size distributions of the microcapsules in the samples of comparative formulations 1, 2 and 8 and formulation 11 according to the invention stored at different temperatures for time periods of 2 weeks and 4 weeks were determined using a Malvern Mastersizer 2000 light scattering particle sizer fitted with a small volume sample unit and using software version 5.12. Prior to measurement, the samples were shaken or stirred to ensure homogeneity.
  • a comparison of the particle size measurements ( ⁇ m, mean/90%) of the initial formulations and the samples stored at different temperatures for time periods of 2 weeks and 4 weeks are shown in Table 3.
  • Table 3 the change in particle sizes in each of comparative formulations 1, 2 and 8 and formulation 11 according to the invention was substantially consistent in the samples stored under substantially the same conditions.
  • Viscosities were determined for the samples of comparative formulations 1, 2 and 8 and formulation 11 according to the invention stored at different temperatures for time periods of 2 weeks and 4 weeks using a AR1000 viscometer from TA Instruments (New Castle, DE). A comparison of the viscosities in mPas (up/down at 100 s -1 ) and syneresis (measured as the percent top clearing) of the initial formulations and the samples stored at different temperatures for time periods of 2 weeks and 4 weeks are shown in Tables 4 and 5.
  • Table 4 Determination of Viscosity of Insecticidal Capsule Formulations Formulation Time Temperature 1 2 8 11
  • formulation 11 according to the invention demonstrated substantially improved syneresis after storage at different temperatures for time periods of 2 weeks and 4 weeks in comparison to the amount of syneresis observed of comparative formulations 1, 2 and 8.
  • Example 3 Chlorpyrifos-methyl Degradation as a Function of Molar Ratio of Amine:Isocyanate Groups in the Cross-linking Amine and Isocyanate Monomer Emulsion Used to Prepare Insecticidal Capsule Formulations
  • the amount of the chlorpyrifos-methyl in the samples stored at 54°C, 40°C, FT and RT were determined after 2 weeks and the amount of the chlorpyrifos-methyl in the samples stored at 40°C and RT were determined after 4 weeks.
  • Table 6 shows the amounts (in wt%) of the chlorpyrifos-methyl in each of the samples stored for the times and at the temperatures described.
  • FIG. 1 is a bar graph showing loss (in wt%) of chlorpyrifos-methyl in comparative formulations 1, 2 and 8 and formulation 11 according to the invention as a function of the molar ratio of amine:isocyanate groups in the cross-linking amine (EDA) and isocyanate monomer (PAPI® 27) emulsion used to prepare the insecticidal capsule formulations following 2 weeks storage at 54°C.
  • Comparative formulation 1 (molar ratio of amine:isocyanate groups of about 1.15) exhibited a chlorpyrifos-methyl loss of about 4 wt%.
  • Comparative formulation 2 (molar ratio of amine:isocyanate groups of about 1) exhibited a chlorpyrifos-methyl loss of about 2.5 wt%.
  • Comparative formulation 8 (molar ratio of amine:isocyanate groups of about 0.9) exhibited a chlorpyrifos-methyl loss of about 1.5 wt%.
  • Formulation 11 according to the invention (molar ratio of amine:isocyanate groups of about 0.7) exhibited a chlorpyrifos-methyl loss of about 0 wt%.
  • Table 6 Determination of Chlorpyrifos-methyl (wt%) in Insecticidal Capsule Formulations After Storage at Various Temperatures Formulation Time Temperature 1 2 8 11 Initial RT 20.2 20.3 20.3 20.1 2 weeks 54°C 19.4 19.8 20.0 20.2 2 weeks 40°C 20.1 20.2 20.1 20.2 2 weeks FT 19.2 20.1 20.0 19.9 2 weeks RT 20.2 20.2 20.3 20.1 4 weeks 40°C 19.8 20.1 20.2 20.3 4 weeks RT 20.3 20.3 20.1 20.0
  • Example 4 Chlorpyrifos-methyl Degradation as a Function of Capsule Wall Thickness While Maintaining the Molar Ratio of Amine:Isocyanate Groups in the Cross-linking Amine and Isocyanate Monomer Emulsion Used to Prepare Insecticidal Capsule Formulations at About 0.5:1.
  • Formulations of chlorpyrifos-methyl were formed using substantially the same methods described in Example 1.
  • Formulations A, B, C and D included RELDAN® insecticide as the source for the chlorpyrifos-methyl.
  • the formulations were prepared using a molar ratio of amine:isocyanate in the emulsion used to prepare the microcapsules of about 0.5:1.
  • the microcapsules of formulations A, B, C and D each had a particle size of about 3 ⁇ m and, respectively, had wall thicknesses of about 5 nm, about 10 nm, about 20 nm and about 100? nm.
  • formulations A, B, C and D The pH and loss of chlorpyrifos-methyl content of formulations A, B, C and D were determined over time. The properties were determined immediately after formation ("Initial"). Samples of each of the formulations A, B, C and D were stored at 54°C and at room temperature (RT, about 25°C). The properties of the samples were determined after 2 weeks in storage, after 4 weeks in storage and after 6 weeks in storage. Tables 7 and 8 provide data showing a comparison of each of the properties in formulations A, B, C and D observed after storing each of the formulations as described.
  • the loss of chlorpyrifos-methyl content in the samples of formulations A, B, C and D stored at different temperatures for time periods of 2 weeks, 4 weeks and 6 weeks were determined using conventional methods.
  • a comparison of the loss of chlorpyrifos-methyl content in the samples of formulations A, B, C and D of the initial formulations and the samples stored at different temperatures for time periods of 2 weeks, 4 weeks and 6 weeks are shown in Table 7.
  • the loss of chlorpyrifos-methyl content in formulations A, B and C stored at 54°C was substantially greater than for sample D after time in the samples stored under substantially the same conditions.
  • reducing the microcapsule wall thickness in each of formulations A, B and C may increase the loss of chlorpyrifos-methyl content in those samples.

Claims (18)

  1. Formulation d'insecticide, comprenant :
    une enveloppe polymère formée à partir d'un mélange comprenant une amine de réticulation et un isocyanate, le rapport molaire des groupes amino:isocyanate étant compris entre 0,3:1 et 0,8:1 ;
    un insecticide au moins partiellement encapsulé par l'enveloppe polymère ; et
    une phase aqueuse continue, l'amine étant choisie dans l'ensemble constitué par l'éthylènediamine (EDA), la tétraméthylènediamine et la 1,2-cyclohexyldiamine.
  2. Formulation d'insecticide selon la revendication 1, dans laquelle l'amine est l'éthylènediamine.
  3. Formulation d'insecticide selon la revendication 1, dans laquelle l'insecticide comprend un organophosphate choisi dans l'ensemble constitué par : l'acéphate, l'azinphos-méthyle, le chlorfenvinphos, le chloréthoxyfos, le chlorpyrifos-méthyle, le diazinon, le diméthoate, le disulfoton, l'éthoprophos, le fénitrothion, le fenthion, le fénamiphos, le fosthiazate, le malathion, le méthamidophos, le méthidathion, l'ométhoate, l'oxydéméton-méthyle, le parathion, le parathion-méthyle, le phorate, le phosmet, le profénofos et le trichlorfon, de préférence dans laquelle l'insecticide comprend le chlorpyrifos-méthyle.
  4. Formulation d'insecticide selon la revendication 1, dans laquelle le rapport molaire des groupes amino aux groupes isocyanate dans l'amine de réticulation et le monomère isocyanate vaut 0,7 : 1.
  5. Formulation d'insecticide selon la revendication 1, dans laquelle l'enveloppe polymère a une épaisseur comprise entre 2 nm et 20 nm.
  6. Procédé de préparation d'une formulation d'insecticide, comprenant les étapes consistant à :
    réunir une phase aqueuse et une phase huileuse comprenant un monomère isocyanate et au moins un insecticide ;
    émulsifier la phase huileuse et la phase aqueuse pour former un mélange ;
    ajouter une amine de réticulation au mélange, le mélange comprenant un rapport molaire des groupes amino aux groupes isocyanate compris entre 0,3:1 et 0,8:1 ; et
    faire réagir le monomère isocyanate avec l'amine de réticulation pour former la formulation d'insecticide, l'amine étant choisie dans l'ensemble constitué par l'éthylènediamine (EDA), la tétraméthylènediamine et la 1,2-cyclohexyldiamine.
  7. Procédé selon la revendication 6, comprenant en outre les étapes consistant à :
    - dissoudre dans de l'eau un ou plusieurs composé(s) parmi un tensioactif et un conservateur, pour former la phase aqueuse, de préférence la dissolution d'un ou plusieurs composé(s) parmi un tensioactif et un conservateur pour former la phase aqueuse comprenant la dissolution de poly(alcool vinylique) et d'un conservateur dans de l'eau, ou
    - réunir un monomère isocyanate, du 1-nonanal et une solution comprenant du chlorpyrifos-méthyle dans un solvant pour former la phase huileuse, le monomère isocyanate étant de préférence un polyméthylène polyphénylisocyanate.
  8. Procédé selon la revendication 6, dans lequel
    - l'étape consistant à émulsifier la phase huileuse et la phase aqueuse pour former un mélange comprend l'émulsification de la phase huileuse et de la phase aqueuse pour former une pluralité de particules de la phase huileuse dans la phase aqueuse,
    - l'étape consistant à ajouter une amine de réticulation au mélange comprend la formation du mélange réactionnel pour l'obtention d'un rapport molaire des groupes amino aux groupes isocyanate égal à 0,7 : 1, ou
    - l'étape consistant à faire réagir le monomère isocyanate hydrophobe avec l'amine de réticulation pour former la formulation d'insecticide comprend l'exposition du monomère hydrophobe et de l'amine de réticulation à une température comprise entre 20 °C et 60 °C.
  9. Procédé de préparation d'une formulation d'insecticide, comprenant les étapes consistant à :
    former une phase huileuse consistant en un monomère isocyanate hydrophobe, au moins une composition d'insecticide, un solvant et un conservateur ;
    réunir la phase huileuse avec une phase aqueuse pour former un mélange ; et
    réunir au moins une amine de réticulation avec le mélange pour former la formulation d'insecticide,
    l'amine étant choisie dans l'ensemble constitué par l'éthylènediamine (EDA), la tétraméthylènediamine et la 1,2-cyclohexyldiamine, et
    le rapport molaire des groupes amino aux groupes isocyanate étant compris entre 0,3:1 et 0,8:1.
  10. Procédé selon la revendication 9, dans lequel
    - l'étape consistant à former une phase huileuse consistant en un monomère isocyanate hydrophobe, au moins une composition d'insecticide, un solvant et un conservateur comprend la formation d'une phase organique consistant en un monomère isocyanate, du chlorpyrifos-méthyle, un solvant et du 1-nonanal ; ou
    - l'étape consistant à réunir la phase huileuse avec une phase aqueuse pour former un mélange comprend l'émulsification de la phase huileuse et de la phase aqueuse pour former une pluralité de particules de la phase huileuse dans la phase aqueuse, de préférence l'émulsification de la phase huileuse et de la phase aqueuse pour former une pluralité de particules de la phase huileuse dans la phase aqueuse comprenant l'émulsification de la phase huileuse et de la phase aqueuse pour former une pluralité de particules ayant un diamètre moyen compris entre 1 µm et 30 µm.
  11. Procédé selon la revendication 9, comprenant en outre le choix d'un polyméthylène polyphénylisocyanate en tant que l'isocyanate.
  12. Procédé de préparation d'une formulation d'insecticide, comprenant les étapes consistant à :
    réunir l'insecticide, une amine de réticulation et au moins un monomère isocyanate, les groupes amino et les groupes isocyanate étant présents en un rapport molaire compris entre 0,3:1 et 0,8:1 ; et
    former une enveloppe polymère qui encapsule au moins partiellement une partie de l'insecticide,
    l'amine étant choisie dans l'ensemble constitué par l'éthylènediamine (EDA), la tétraméthylènediamine et la 1,2-cyclohexyldiamine.
  13. Procédé selon la revendication 12, dans lequel
    - l'étape consistant à réunir l'insecticide, une amine de réticulation et au moins un monomère isocyanate comprend la réunion d'un organophosphate, de l'amine de réticulation et dudit au moins un monomère isocyanate, ou
    - l'étape consistant à former une enveloppe polymère qui encapsule au moins partiellement une partie de l'insecticide comprend :
    la formation d'une phase huileuse comprenant l'insecticide et ledit au moins un monomère isocyanate ;
    la réunion de la phase huileuse avec une phase aqueuse pour former un mélange ; et
    la réunion de l'amine de réticulation avec le mélange pour former la formulation insecticide microencapsulée, de préférence la formation d'une phase huileuse comprenant l'insecticide et ledit au moins un monomère isocyanate comprenant la formation d'une phase huileuse consistant en l'insecticide, ledit au moins un monomère isocyanate et un solvant, ou
    la réunion de la phase huileuse avec une phase aqueuse pour former un mélange comprenant la réunion de la phase huileuse avec une phase aqueuse comprenant de l'eau et un tensioactif pour former le mélange.
  14. Procédé selon la revendication 12, dans lequel l'insecticide est le chlorpyrifos-méthyle.
  15. Procédé pour la lutte contre une population d'insectes, comprenant :
    la préparation d'une formulation d'insecticide, comprenant :
    la réunion d'une phase aqueuse et d'une phase huileuse comprenant un monomère isocyanate hydrophobe et au moins un insecticide pour former un mélange ;
    l'addition d'une amine de réticulation au mélange réactionnel, le mélange réactionnel comprenant un rapport molaire des groupes amino aux groupes isocyanate compris entre 0,3:1 et 0,8:1 ; et
    la mise en réaction du monomère isocyanate hydrophobe avec l'amine de réticulation pour former la formulation d'insecticide ; et
    l'application de la formulation d'insecticide sur une aire contenant une population d'insectes ou adjacente à celle-ci,
    l'amine étant choisie dans l'ensemble constitué par l'éthylènediamine (EDA), la tétraméthylènediamine et la 1,2-cyclohexyldiamine.
  16. Formulation aqueuse, stable, d'insecticide, comprenant :
    a) une microcapsule, comportant une paroi d'enveloppe polyurée insoluble dans l'eau, préparée par une réaction de polycondensation interfaciale entre une amine de réticulation soluble dans l'eau et un monomère isocyanate soluble dans l'huile, dans laquelle
    (i) le rapport molaire des groupes amino aux groupes isocyanate est compris entre 0,3:1 et 0,8:1,
    (ii) l'enveloppe polyurée a une épaisseur de plus de 2 nanomètres (nm) et moins de 50 nm,
    (iii) la taille moyenne de particule vaut d'environ 1 micromètre (µm) à 30 µm, et
    (iv) contenant un noyau liquide interne comprenant un insecticide au moins partiellement encapsulé par l'enveloppe polymère ; et
    b) une phase aqueuse continue,
    l'amine étant choisie dans l'ensemble constitué par l'éthylènediamine (EDA), la tétraméthylènediamine et la 1,2-cyclohexyldiamine.
  17. Formulation d'insecticide selon la revendication 16, comprenant en outre un tensioactif.
  18. Formulation d'insecticide ou procédé selon les revendications 1, 6, 9, 12, 15 ou 16, dans laquelle/lequel l'insecticide inclut au moins un insecticide organophosphate.
EP12744477.6A 2011-02-11 2012-02-10 Formulations insecticides améliorées Active EP2672817B2 (fr)

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